Condensation product and method of preparing and using same



Jan. 1s, 1944.

E. LIEBER ET AL CONDENSATIQN PRODUCT AND METHOD OF PREPARING AND USING SAME AFiled Oct. 28, 1941 w n V, n .s N P D T y m 7, n m c m .mqowo MM50 s 2 5 V v P R u o p UQRWHWQK0 LwWQSsx Xhab w 0 0 0 u w 4 p.. s 4.

//scos/TY INDEX Patented Jan. 18, 1 944 CONDENSATION PRODUCT AND BIETHOD F `1RE1ARll\T(.3`r AND USING SAME Eugene Lieber, West New Brighton,` Staten Island, N. Y., and Martin M. Sadlon, -Roselle y Park, N. J., assignors, by mesne assignments, to Standard Catalytic Company, a corporation of Delaware Application October 28, 1941, Serial No. 416,827

14 Claims.

The present invention relates to a novel type of chemical condensation product and to methods of preparing and usingsame; and more partic- --lot 252-59) y .n

'the percent vby weight of the chlorine in the ularly it relates to the production of a product having both the property of reducing thepour point of waxy mineral lubricating oils and also the property of improving the viscosity index of various other hydrocarbon oils and speciilcally mineral lubricating oils.

' In our previous Patent 2,174,246 it was disclosed that the Friedel-Crafts condensation of chlorinated paraffin wax and aromatic compounds, such as naphthalene, could best be carrled out for the production of pour depressors for waxy lubricating oils by mixing the nephthalene with the aluminum chloride in a halogenated hydrocarbon solvent, such as tetrachlorethane, and then adding chlorinated wax thereto, the reaction temperature being maintained between about room temperature and 200 F. In that patent, the amount of catalyst to be used is broadly stated as 1-5%, or more, andthe amount of chlorine in chlorinated wax is broadly stated as lll-%, or more, although the only speciilc amount of aluminum chloride disclosed is 1.4% and the only specic chlorine contents stated are 11%, 13% and 15%. The products prepared were shown to be good pour depressors for waxy lubricating oils.

It has now been found that by using the same general process but by increasing the reactivity as controlled by the chlorine content of the chlorinated wax andthe amount of aluminum-chloride catalyst, condensation products can be made sludge-dispersing properties.- -These and other f advantages of the invention-will be more fully understood from the vfollowing description.

VBroadly, the invention comprises using for the condensation process described above a chlorinated wax having a chlorine content of at least 15%,. and preferably 20% to 30%. and an amount of aluminum chloride between the approximate limits of 0.5 and 5.0%, with the important additional requirement that the arithmetical product o f the percent of catalyst. based on the weight of chlorinated wax, times the square of chlorinated wax should be at least 400. Although the exact mechanism of chemical reactions involved in this process is not well understood, it is believed that the success of the process depends to a substantial extent upon the use of a sumcient amount of aluminum chloride catalyst to cause proper` reaction of the trichlorwax molecules in the chlorinated wax used as raw material. Examination of chlorinated waxes containing various amounts of chlorine indicates that although there is lsome trlchlor product present with monoand dichlor waxes in mixed products containing less than about 15% C1, yet when the chlorine content is 15% or above the relative proportion of monochlor and dichlor waxes decreases sharply with a. correspondingly great 'increase in the proportion of trichlor wax so .that in chlorinated waxes containing 15% -or over of chlorine the trichlor substituents are present in prepondering amount and at approximately 20% Cl content there is about '15% lo f trichlor substituent present. When the chlorine content reaches as high as 25%, there ls relatively little monoor di-substituent present. This is shown in the' following table.

Distribution of chlorinated products in a calm-mated 118 hmmag-,pam waa.-

This table represents an analytical distribu` .tion study of chlorinated wax. The analyses were carried out by low temperature tractionation using acetone as a solvent.

In carrying out the present invention a large number of materials has been tested and found successful. In the class of aromatic compounds, napthalene'has given outstandingly superior results and accordingly it is the preferred aromatic material to be used. However, other aromatic compounds have given fairly goodresults, especially with control of reaction'conditions such as by the use of a relatively low proportionof solvent and a high proportion of catalyst, without, however, using very elevatedtemperatures unlessnecessary. Thus other aromatic compounds which may be used include benzene, pher'ioL.

beta-naphthol, diphenylene oxide, polymers of dihydronapthalene, such as a tetramer thereof,

analogous or equivalent thereto, as well as mixtures of two or more aromatic compounds, such,` for instance, as found in coal tar fractions containing naphthalene, anthracene, and other polynuclear aromatic hydrocarbons and derivatives best catalyst both from the point of view of cost 15f and efficiency, other Friedel-Crafts catalysts may be used if desirable,such as ferric chloride,

titanium tetrachloride, boron chloride, or'boron fluoride, or their mixtures.

very reactive, and preferably should range from room temperature to 150 F. The reaction time may vary over a fairly wide range depending upon the amount of catalyst and solvent as well as the reaction temperature but normally it should be within the approximate limits of 5 minutes and hours, and preferably range from 1/4 hour to 5 hours. f

cosity of the reaction mixture and/or the cessa- L tion of the liberation of any hydrogen chloride,

The low molecular weight halogenated hydrocarbon solvent should be one which is inert under the condensation reaction conditions used. Preferably it should be a chlorinated hydrocarbon having not' more/'than 4 carbon atoms and preferably containing 3 or more halogen atoms.

Tetrachlorethane has been found to be especially suitable, although dichlor, benzene, trichlorethane, ethylene dichloride trichlor benzene, etc., may be used, if desired. Although this solyent does not actually enter into the chemical condensation reaction, nevertheless it has a dennite inuence on the course of the reactions bethe reaction mixture is then, for convenience, diluted with vadditional solvent, such as refined "kerosene, orxa chlorinated hydrocarbon solvent,

such as tetrachlorethane or ethylene dichloride, and neutralized or hydrolyzed by adding water or an aqueous solution of caustic soda, or alcohol or any other suitable hydrolyzing agent or mixture of two or more of them. After the settling and removal of the sludge layer, the reaction product is then subjected to distillation, starting at either normal or reduced pressure, but in any case completing the distillation under substantially reduced pressure, such as by using fire and steam distillation or by vacuum distillation, in order to obtain the desired high molecular weight distillation residue, without causing any substantial cracking.` If vacuum distillation is used, it may be controlled to an absolute pressure of between about 5 and 100 Another important requirement for carrying `4,0

out the present invention is the proper order of adding the ingredients, namely, the chlorinated l Wax must be added last in order to avoid formation of oil-insoluble condensation products when starting with a chlorinated wax containing 20% or more of chlorine.

The Iproportions of aromatic compound and chlorinated wax may be varied over a fairly Wide range without seriously interfering with production of the desired viscosity-index improving property. For instance, usually from- 1-10 mols of chlorinated wax may be used for one mol of aromatic compound, preferably about 3-8 mols of chlorinated'wax may be used for one mol of aromatic compound. Since chlorinated wax is probably the most important raw material and is generally used in large amounts, one of the easiest ways to calculate the amount of various raw materials to be used is to base all calculations on 100 parts by weight or by volume of chlorinated wax and in such a case the preferably about 10 to l5 parts in the case of amount of aromatic compound to be used should range from about 5 to 3 0 parts by weight, or

naphthalene`.\ On this saine basis, when using 100 parts of chlorinated wax by weight, the alirminum chloride or other catalyst to be used should be about 0.5 to 5.0%, or preferably about 1-3%\. The amount of chlorinated hydrocarbon solvent to be used should be about 10 to 200 volnmes, or preferably 20 to 100 volumes, for each 100 volumes of chlorinated wax.

The reaction 'temperature should be maintained below 200`F., except in a few particular instances where the aromatic compound-is not `75 when used in small amounts, such as 0.1% or millimeters of mercury, preferably about 10 to 50 millimeters.

nal temperature to which the distillation is carried should be at least 350 F., and preferably at least 400 F., and it may be 500 F. or 600 F.

A few tests indicated that a vacuum distillation under an absolute pressure of about 20 to 50 millimeters of mercury carried up to a temperature of 330 F. gave distillation results substantially equivalent to fire and steam distillation carried up to about 380 or 400 F. If desired, the condensation product may be recovered as a blend in heavy lubricating oil, preferably a naphthem'c base oil, by adding a small amount of a suitably high-boiling fraction to the reaction product just prior to or during the distillation.

l The condensation product per se is a dark, viscous liquid soluble in hydrocarbon oils. As it undoubtedly is not all one single-compound but is probably a mixture of a number of different compounds having slightly different structure, the mixed product may, if desired, be separated into different fractions by various suitable means, such as distillation. solvent extraction, etc., in order to recover one or more fractions which are especially potent in regard to viscosity-index improvement and/or pour depressing as well as oxmation-inhibiting and sludge-dispersing characteristics. The amount of addition agent to be used in lubricating oils may vary over a fairly wide range, such as from about 0.5% to 10% when it is desired to effect a substantial improvevantage of this novel product, especially in contrast to any products of the prior art, is that it not only has good pour-depressing properties Usually, whether fire and steam; 5, distillation is used or vacuum distillation, the

pressors are effective only in amounts less than..

1% or 2% and are either ineffective or in some cases raise the pour point of the lubricating oil base stock when used in concentrations as large as 3%, 5%, 7%, or 10%.

The lubricating oil base stock to which thev new condensation products of this invention may be added may be any of the common types capable of improvement either in respect to viscosity-index or lowering of the pour, point, or both, such as Pennsylvania type oils or other oils of a parafiinic nature, or West Texas or other types of naphthenic base oils or Mid-Continent or similar mixed base oils. ne may, of course, use any desired particular fractions or others separated from.these various crudes by known methods, such as distillation, solvent extraction, etc., and one may use oil base stocks which have been refined by various known methods, such as, clay-treating, acid-treating` propane dewaxing, etc.

The relative effectiveness of the condensation products of the present invention as compared to several materials of the prior art in regard to their effect-on pour point and viscosity index, are shown in the accompanying drawing which is a chart in which pour point data are plotted on the vertical or Y axis against viscosity index data on the horizontal or X axis. 'I'he lubricating oil base stock used in all of the tests referred to in this chart was a solyent-extracted Mid- Continent type of parailinic oil having a Saybolt viscosity of 44.4 seconds at 210 F., a viscosity index of 114 and a pour point of 5 F.

In this chart four prior art materials are shown by dotted lines. Material A, a commercial pour depressor, when used in a concentration of 0.625% reduced the pour point from 5 to 17 F. and only changed the viscosity index from 114 to 115 and when used in 2.5% concentration gave the same pour point as the plain base stock, namely, 5 F. and still only slightly aiTected the viscosity index from 114 tq 117. Material B, likewise a commercial pour depressor, reduced the pour'point to 15 F. when used in a concentration of 0.25%, but when used in larger amounts, the pour point rose to 10, 5, andv +5 F. when used respectively in concentrations of 0.5%, 0.625%, and 2.5%, the viscosity index in the meantime being only slightly aiected (actually lowered) from 114 to 111 in the 2.5% concentration. Material D, on the other hand, marketed commercially as a viscosity-index improver but also stated to have pour-depressing properties, made substantial improvements in the viscosity index to 144, 15B, and 157, respectively, in concentrations of 0.625%, 1.75% and 2.5%, but had negligible eiect on the pour point until the concentration reached about 1.75% where the blend hada pour point of 15, but then it rapidly raised to F. when the concentration was increased to 2.5%.

In strict contrast to the above prior art materials the novel condensation products of the present invention, several of which are identied b K solid lines on the chart as X1, X2, etc., have reduced the pour point to as low as 25 F. and in some cases to v 35" F., or lower, when used in concentrations of 2.5%, or insome cases as low as 0.625%, while at the same time eiecting a very substantial increase in viscosity index from 114 3 .to values ranging from 125 to 145, depending upon the particular sample tested. Thus, for instance, material'Xiwhen used in concentration of 0.625% lowered the pour point to 25 F. and raised the viscosity index to 120, and in 2.5% concentration lowered the pour point still furtherto below 35 F. (the test was stopped at 35, although the solid point had still not been reached) and the viscosity index was raised further to 135. It is interesting to note that\this same material when used in even higher concentration (5%) still produced a. pour point below 35 F. and'raised the viscosity index still higher to 143. Another sample -of`the product of this invention, &, showed a pour point of below 35 F. in concentrations of both 2.5% and 5.0% and showed a viscosity index of 131 and 139 for those same two concentrations; Another sample, X3,l produced pour points below 35 F. for both 2.5% and 5.0% concentrations and gave a viscosity index of 127 and 134 forthose same con-R centrations. Itis apparent that these threel samples, Xi, X2. and Xa, are all extremely potent pour depressors while at quite effective viscosity-index improvers. other hand, samples quite as potent in.po samples Xi, X2, and Xs On the -depressing properties as because in both the 2.5% and the 5.0% concentrations the X4 gave a pour point of 30 F., and X5 gave a pour point of 25 F., but are somewhat superior thereto in respect to viscosity-index improvement because X4 and X5 both produced a viscosity index of 137 in a 2.5% concentration and 144 in a 5.0% concentration. l

It is thus obvious that the products of this invention are in an entirely dilTerent iield than the products of the prior art. Also it ls evident both fromvthe data referred to above, plotted graphically on the drawing, and to the additional tabulated data to be discussed later, that the present invention oiers wide possibilities for making products having various, desired, controlled ratios of pour-depressing and viscosity-index iniproving properties by properly adjusting the proportions of raw materials and the reaction conditions. It is believed that the possibility of obtaining products having such a wide range of characteristics is due primarily to the fact that the trichloro-substituted Wax molecule is capable of condensing in what might be termed "threedimensional directions. It is probable that the relative amount of pour-depressing and viscosityindex improving properties imparted to the condensation product depend to some extent, at

least,l upon the relative amount of linear type -and cyclic or mesh type of condensation-and that this latter type in turn depends primarily upon the proportion of trichloro substituents in the chlorinated wax and upon the amount of aluminum chloride, although undoubtedly the temperature, kind and amount of solvent and the reaction time have also some eiect upon the chemical structure of the resulting condensation product.

The products of this invention are not only useful for improving the viscosity index and the pour point of lubricating oils having relatively y e high viscosity index,

but are also useful for improving the viscosity index of oils having a relatively low viscosity index, such as 50, 100, etc. The following table shows the effect on viscosity index and viscosity at 210 F. of various amounts of the condensation product of this in-L vention in two dinerent low V. I. oils: (1) an ink the same time being 4 and X5 are perhaps not Improvement in low V. I oils In addition to the primary use suggested above for the products of this invention, namely, as addition agents to mineral lubricating oils, it is also possible to use them as addition agents in other 20 fects, or in substantially larger amounts, e. g., 25

from 1% to 10%, or so, for raising'the viscosity` index or otherwise improving the oils. If desired, these products may also be used as dewaxing aids for assisting in the removal of wax from lubricating'oil stocks containing large amounts ot paraiiln wax.

In order to show more clearly the effect of various proportions of raw materials and the effect of various reaction conditions on the chemical reactions involved in the present invention, the following table of experimental data is given. In all of these tests the aromatic compound, aluminum chloride, and the solvent were iirst mixed together in a suitable reaction container and then the chlorinated wax was added last, in each case using 600 cc. of chlorinated wax. The tests are tabulated primarily in order, with those using naphthalene first as indicated in column 2, and .those using the least amount of naphthalene as in column 3, and then the tests using the same amount of naphthalene are in order according to the melting point of the wax used for making the chlorinated wax, as indicated in column 4, ranging from the lowest to the highest, and similarly the tests made with a wax of any one melting point, such as 121 F., are then further arranged according to the percentage of chlorine in the chlorinated wax, as indicated in column 5, ranging from the lowest amount of chlorine to the highest, and using the same order of arrangement as to the remaining columns having to do with raw materials andreaction conditions or procedure, namely, columns 6-13.

Table Aromatic Cl-wax Reaction Distiliation Solvent RunNo. Wax P t T. o E. A1?" Vac Sm M H er cen cc. c m ax., rs. Kind G C1 F. Hrs. F.on DE hem 121 234 l0 125 A 121 234 10` 125 4 114 21 176 8.2 125 6 114 21 234 7.2 125 5 114 21 234 8.2 125 5 114 21 234 15.0 125 5% 114 21 351 15 125 3 114 21 351 20 125 3 114 21 351 20 125 3 114 2l 351 25 125 3 121 1e 29o 17 125 S 121 `19 290 17 85 2 121 19 290 17 125 4 121 21 175 11 125 1% 121 21 234 S 125l 1% 121 21 234 8 125 2-3 121 21 234 8 125 2-3 121 21 234 8 125 2-3 121 21 234 8 125 2-3 121 21 234 8 125 2-3 121 21 234 S 125 2-3 121 21 234 8 125 2-3 121 21 234 8 125 121 21 234 8 125 121 2l 234 10 125 121 21 234 10 125 121 2 1 234 15.4 S5 121 21 351 10 125 121 21 351 10 125 121 21 351 15 85 121 21 351 15 85 121 21 468 15 125 121 2l 468 20 125 121 2l 585 10 125 121 25 234 10 125 121 25 468 20 85 121 25 468 20 85 121 26 175 7 125 121 26 234 7 125 133- 21 V234 8 125 133 21 351 8 125 133 21 468 15 125 142 21 351 8 125 142 21 351 8 125 1 146 21 468 10 125 146 21 585 10 125 1 146 26 527 10 125 1 121 21 Z114 10 125 1 x 121 25 234 10 125 1 x 121 21 234 22 125 5 x 121 21 wir 15 325 5 x 121 21 291 17 125 1% x 121 21 234 22 125 5 x 127 21 234 33 125 6 x 135 21 354 33 -150 5 x 2,556,466 E ITable-(iontinuee! y 2.5% cono. 6.0% conc. Run No. Yield, g Remarks i VT4-[21 v.r.114 .1113 via/21o v r 1210 585 47.9 55.6 142 338 52.4 55.1 135 498 47.0 50.2 129 364 47.9 53.5 129 319 46.9 49.9 124 376 49.6 57.2 130 525 4&3 54.0 134 552 49.8 56.7 135 516 50.3 00.5 139 533 23'3 'i i' 1.25 =123v. 462 49.5 55.7 134 7 I 30p p 462 48.2 51.9 127 392 46.7 49.3 129 59 31 5 Li htnin mi r. 245 48.8 54.2 g g e 215 47.7 51.7 193 46.7 49.6 252 49.1 55.4 243 4&6 53.6 34 31 32 I 1.25 4 524 48.3 .52.8 l2 V I 20p p 536 48.8 55.3 28o 50.1 V56.4 554 50.6 .52.5 286 51.9 64.1 'i 235 Lightning mixer. 532 47.5 51.5 Anchor ier. 312 483 53.6 mx 254 51.4 62.2 525 59.7 59.3 532 48.9 55.1 9s 3f -L D i htnin ix r. 435 48.7 53.5 g gm e 379 48.4 53.0 495 50.4 57.1 472 50.3 58.8 608 51.5 63.2 554 49.2 55.8 480 50.8 58.9 548 50.2 59.4 542 52.1 66.2 554 51.4 63.9 417 49.1 54.4 532 48.9 55.1 223 47.1 50.6 300 47.1 48.4 208 48.3 52.6 349 47.5 51.3 424 49.9 57.6 455 50.1 54.7

1 Miscellaneous aromatic materials: A-B-naphthol-CwHlOH B=Tetramer of dihydronaphthalene C=Diphenyl In the above table it isapparent that a wide variation in raw materials and reaction conditions can be used to obtain wax-aromatic condensation products having the novel feature of being good viscosity-index improvers, and at the same time most of those products which have been tested for Dour-depressing property are also found to be potent pour depressors even in the relatively large amounts, such as 2.5% and 5.0% used for obtaining viscosity-index improvement. A comparison of certain individual tests indi- :ates to some extent how the proportions of ma- :erials and reaction conditions affect the yield ind nature of theresulting products. For in- ;tance, in tests 4 and 5 all of the factors repre- :ented in columns 2-13 were identical, except in :olumn 7 where the amount of aluminum chloide is shown as 7.2 grams in test 4, and 8.2 rrams in test 5, and accordingly the indications .rethat the slightly lower amount of aluminum hloride resulted in a slightly higher yield (364 .s compared to 319 grams), a slightly higher visosity at 210, and a slightly higher viscosity index 124 as compared to 120 in 2.5% concentration. nd 129 as .compared to 124 in 5.0% concentraion). It should be kept in mind, however, that ich a specic conclusion must be considered as eing valid only when all of the other factors 35 of to 600 represented in columns 2-6 and 8-13 are maintained .as are reported. For instance, in tests 7 im and 8, where a larger amount of solvent (351 cc.)

was used as compared to 234 cc. in tests 4 and 5, where the reaction time was 3 hours instead of 5 hours, and where the product was recovered by steam distillation to 500 F. for 1A hour instead F. for 2 hours, all of the reaction factors were identical for both tests 7 and 8, except for the amount of aluminum chloride reported in column 7, which in this instance showed that compared to 15 grams of aluminum chloride a (m slightly larger amount, namely, 20 grams resulting in a. slightly higher yield, slightly higher viscosity at 210, slightly higher viscosity index and denitely better pour point (lower). Although this specific conclusion might at first appear contradictory to that made above in respect to tests 4 and 5, both conclusions can be considered cor roborative on the basis that the solvent used. has the eilect of diluting the. catalyst; and therefore, in tests 'I and 8 when a liberal amount of soi- 'vent is used, then a larger amount of. catalyst must be used for best results, and perhaps the 8.2 g.- under the conditions of test 5 is relatively a larger quantity than even 20 g. under the conditions of test 8.

From the results of tests 16-22, it is apparent compared to 114 to '121 F.;

reported in columns 2-9, the best results in viscosity-index improvement are obtained by not carrying the maximum distillation temperature much above 400 F. when using iire andsteam distillation, and keeping it evenslightly lower when using vacuum distillation at 20-50 millimatic compound toy chlorinated wax have relatively 'less influence on the yield and. nature of the resulting products than do some of the otherl factors listed in columns 4-13;

(3) That good results in viscosity-index improvement as well as in pour-depressing properties can be obtained withchlorinated wax Vderived fom paraiiin wax having a melting point ranging anywhere from 114 to146i1i., with perhaps slightly better results obtained from the higher melting point waxes, e. g., 130 to 146 (4) That fairly good results in both viscosityindex improvement and pour-depressing have been obtained with chlorinated waxes containing 16% and 19% of chlorine, providing a sufiicient amount of aluminum chloride (e. g., about 2.5%

or more) is used; in general, either better results are obtained or good results are obtained in an easier manner by the use of chlorinated wax containing substantially more than v20% or chlorine, `such as 21%. 25%, or 26%:

(5) Usually within reasonable limits, the less solvent the more potent will 'be the viscosity index of the product, although, of course, there are exceptions in cases where substantially larger amounts of catalyst were used, or some otherv factor was substantially varied;

(6) It appears that the principal effects of raising the temperature fromy 85"4 to 125 F. is tov speed up theA chemical reaction activity in general, but it should also be -mentioned that, from other tests not reported, it has beenfound that when using naphthalene as the aromatic compound, as the temperature is raised above 150 F., the viscosity-index improving` potency is gradually reduced, which is probably due to the acceleration of side reactions or the production of undesirable condensation products;

"(7) Since some of the best results were obtained with a reaction time as short as 1/2 hour as in test 42, or even 1A hour, as in test 40, and yet fairly good results have also been obtained with a reaction time of 2 hours as in test 41, and 3 hours in test 29,\it is apparent that the optimum .reaction time depends to a substantial extent upon some of the other important factors, such as the temperature, the amount of aluminum chloride and the volume ofsolvent;

(8) In some cases it has appearedbest to use a mixing apparatus having a revolving blade which scrapes adhering material away from the side walls, rather than merely mixing a relatively small volume of liquid in the interior part of the body of the reaction liquid. This is probably especially true in cases where either due to the high viscosity of the condensation product being formed, or due to the relatively low volume of solvent used, the reaction liquid has become exceedingly viscous.

.that with the materials and reaction conditions Inspection of the results tabulated in the above table also show that the products of this invention produce a relatively large increase in viscosity index for any particular increase in viscosity at 210 E.; this is important because it is desirable to eect as great a rise in viscosity index as possible with the least amount of actual thickening.r

Although .in the above table -the pour test data are all given in respect to a single oil base stock having al pour point of 5 F., the products of this invention are potent pour depressors in general and may be used with lubricating oil base stocks of various types, such as those derived:.from various crudes by distillation, solvent extraction, etc., and'.` also base stocks obtained by dewaxing treatments of waxy oil stocks to various pour points,- such as +30 F., +10 F., 5 F., etc;

Tests indicate that the novel condensation products of this invention also showrelativelyv good resistance to viscosity breakdown under severe mechanical working conditions.

Ina carbonfblack'dispersion test which has beenrecognized as fairly indicative of sludge, dispersing properties, the novel condensation product of this invention was found to be quite effective, andin fact, slightly superior to a material heretofore marketed commercially solely for its sludge dispersing characteristics.

Table Cl i1 Daiglerrson earo re Blend cs. after carlorxing hrs.) black/cc.)

after 24 his.

o11A1. 17s N' .Oil re1r+4% commercial sludge dis- W u l on 24. OilleA 1+3.5% of product of this invene 0 tiolL None 28.6

l Reiined mineral oil base stock, S. A. E. 10.

The novel condensation product of this invention also was tested for oxidation-inhibiting effect as determined in the Indiana Life test with the following results, Y

Indiana life -test 1 Prior art commercial viscosity-indexV improver. Thus the present product not only is effective in increasing the hours of life in the I ndiana test and in reducing the amount of varnish formed, but even small amounts of it are relatively quite eiective in that respect even in the presence of substantial amounts of other addition agents, such as the prior ,art commercial viscosity-index improver M, tested both in combination with the present product and also alone for comparlf son.

vIn preparing lubricating oil compositions or \various other \,types of compositions containing the novel condensation products of this invention, other addition agents already known to the art may also be incorporated, if desired, for instance, dyes, soaps, etc., as well as .other materials-having thickening, viscosity-index improving, pour-depressing, anti-oxidant and/011 sludge-dispersing properties.

It is not intended that this invention be unnecessarily limited to the specific materials which have been recited as illustrative of a class, nor unnecessarily by any theory as to the mechanism of the complex chemical reactions involved in this invention, but only by the appended claims in which it is desired to claim all novelty inherent in the invention.

We claim: v

1. The process of condensing a halogenated 'high molecular weight aliphatic material having more than carbon atoms and containing at least of halogen with an aromatic compound to make a higher molecular weight condensation product, which comprises mixing together the aromatic compound, about 0.5-5.0% of a Friedel- Crafts catalyst based on the weight of high molecular weight halogenated aliphatic material, and a low molecular weight halogenated hydrocarbonsolvent inert under the reaction conditions, adding the halogenated high molecular weight aliphatic material and maintaining the mixture at a reaction temperature until the reaction is completed, the arithmetical product of the percent of catalyst, based on the weight of halogenated high molecular weight aliphatic material, times the square of the percent by weight of halogen in the halogenated high molecular weight aliphatic material being at least 400.

2. Process according to claim 1 in which the reaction temperature is maintained betweenthe approximate limitsof 70 and 150 F.

3. Process according to claim 1 in which the halogenated high molecular weight aliphatic material used is a chlorinated paraffin wax containing 15-30% of chlorine.

4. Process according to claim 1, using chlorinated paramn wax containing 21-30% of chlorine,

and 1-5% of aluminum chloride based on the weight of chlorinated paraffin wax.

5. Process according to claim 1 in which the 9. The process which comprises mixing together naphthalene, aluminum chloride and tetrachlorethane and adding thereto chlorinated paraln wax containing about 25% chlorine, using about 3-8 mols of chlorinated wax per mol of naphthalene, about 13% of aluminum chloride based on the chlorinated wax and about 2.0-100 volumes of tetrachlorethane per 100 volumes of chlorinated wax, and maintaining the reaction mixture at a temperature between the approximate limits of Z0-150 F. for a .reaction time of about 1/4 to 5 hours.

10. Process according to claim 9 in which after the reaction, the reaction mixture is hydrolyzed. the catalyst sludge is removed and the reaction products'are distilled under reduced pressure to obtain the desired wax-naphthalene condensation product as distillation residue.

11. Process according to claim 9 in which, after the reaction, the reaction mixture is treated with a hydrolyzing agent, settled and sludge removed therefrom, and the reaction products are distilled under steam distillation to an upper limit between the approximate limits of 400 F. and 600 F. to obtain the desired wax naphthalene condensation product as distillation residue.

12. A lubricant containing a major proportion of a hydrocarbon lubricating oil and a substantial amount of a product made by the process deiined in claim 1.

13. A'lubricating oil composition having a relatively low pour point and a relatively high viscosity index, comprising a major proportion of a hydrocarbon lubricating oil base stock having a relatively low viscosity index anda relatively high pour point and also containing about 0.5% to 10% of a product having viscosity-index improving and pour-depressing properties, made by Friedel-Crafts condensation of an aromatic compound with a halogenated high molecular weight aliphatic hydrocarbon having more than 10 carbon atoms and containing more than 15% of halogen, the arithmetical product of the percent of Friedel-Crafts catalyst, based on the weight halogenated, high molecular weight aliphatic a; of halogenated high molecular weight aliphatic material used is a chlorinated material of which Athe major proportion consists of molecules containing three chlorine atoms.

6. The process which comprises mixing together naphthalene, aluminum chloride and a ing thereto a chlorinated wax containing 1530% of chlorine, the amount of aluminum chloride being about 0.55.0% by weight based on the 55 chlorinated wax, the amount of solvent being 10-200 volumes per 100 volume of chlorinated wax, and maintaining a reaction temperature below 200 F., the-arithmetical product of the percent of aluminum chloride, based on the weight of chlorinated wax, times the square of the percent by Weight of chlorine in the chlorinated wax being at least 400.

7. Process according to claim 6, using 1-10 mols of chlorinated wax containing substantially more than 20% chlorine, 1 mol of naphthalene, 20-100 volumes of inert solvent per 100 volumes of chlorinated wax, and a reaction temperature of about II0-150" F.

8. Process according to claim 6 using about 3-8 mols of chlorinated parailin wax containing 21-30% of chlorine, 1 mol of naphthalene, 20- 100 volumes of tetrachlorethane per 100 volumes of chlorinated wax, and a reaction temperature' of about 'I0-150 F.

hydrocarbon, times the square of the percent by weight of the halogen in the halogenated high molecular weight aliphatic hydrocarbon being at least 400.

14. A lubricating oil composition having a relatively low pour point and a relatively high viscosity index, comprising a major proportion of a hydrocarbon lubricating oil base stock having a relatively low viscosity index and a relatively high pour point and also containing about 0.5% to 10% of a product having both viscosity-index improving and pour-depressing properties made by Friedel-Crafts condensation of an aromatic compound with a halogenatedv high molecular weight aliphatic hydrocarbon having more than 10 carbon atoms and containing more than 15% of halogen, said .product being made by the Process consisting essentially of mixing together naphthalene, aluminum chloride and tetrachlorethane and adding thereto chlorinated parailn wax containing about 25% chlorine, using about 3-8 mols of chlorinated wax per mol of naphthalene, about 1-3% of aluminum chloride based on the chlo- 

